Fibers dyed with water-insoluble azo-dyestuffs



Patented Mar. 3, 1936 [TED STATEg insane FEQEE FIBERS KEYED WE'EIHWATER-=HNSGLUIELE AZQ-DYESTUFJFS Alfred Bergdolt, Cologne-on-the-Rhine,Anton Ossenbeck, Cologne/Mulheim, and Ernst Tietze and Felix Gund,Cologne-on-the-Rhine, Germany, assignors to General Aniiine Works, Inc.,New York, N. Y., a corporation of Delaware No Drawing. Application March25, 1933, Serial No. 662,826. In Germany April l, 1932 8 Claims.

wherein a: and y stand for radicals of the aromatic-, araliphaticoraliphatic series, which are attached to the C-atoms of the carbonylgroups by carbon atoms, and which in case a: and 3 stand for aliphaticradicals may be linked together, R stands for the radical of adiazotized diazotization component suitable for producing azo-dyestuifs,and wherein all nuclei may bear substituents which do not causesolubility in water; :1: and 1!; may stand f. i., for methyl, ethyl,propyl, butyl, phenyl, naphthyl and benzyl. As substituents which may bepresent there are enumerated by way of example alkyl, alkoxy, halogen,and the nitro group, while the sulfonic acid group and the carboxylicacid group are excluded.

As coupling components coming into consideration for the purpose of ourinvention there may be mentioned for example acetylacetone,benzoylacetone, dibenzoylmethane, phenylacetylbenzoylmethane, thehomologues and substitution products thereof.

As diazotization components there may be used all the bases free fromgroups inducing solubility in water generally used in the manufacture ofazo-dyestuffs, for instance, amines of the benzene-, naphthaleneandcarbazoleseries.

Our new dyeings are obtainable in the usual manner by diazotizing aprimary amine and coupling on the fiber with a diketone of the kindreferred to above; thereby generally yellowish to orange shades of goodfastness properties are obtained, the dyeings being dischargeable,yielding clear white discharges.

The invention is illustrated by the following examples, without beinglimited thereto:

Ewample 1.15 grams of dlbenzoylmethane are intimately mixed with. 60cos. of alcohol, 30 ccs. of water and 7.5 ccs. of aqueous caustic sodalye of 38 B. strength and stirred into 900 cos. of water containing 5ccs. of aqueous caustic soda lye of 38 B. strength and ccs. of aqueousTurkey red oil of 50% strength.

Cotton yarn is impregnated in this solution for about half an hour,squeezed, dried, and the dyeing is developed by passing the yarn forhalf an hour into a diazo solution prepared from 22.5 grams of1-methyl-2-amino-4-chloro-S-benzoylaminobenzene, said diazosolutioncontaining 11 cos. of aqueous acetic acid of 50% strength.

The cotton is rinsed, washed, soaped in a boiling bath, washed again anddried. A clear greenish-yellow dyeing of good fastness to boiling andlight is thus obtained, said dyeing being dischargeable, yieldingthereby clear white discharges. The dyestufi corresponds to thefollowing formula:

(His

CHI-O Example 3.--In an'analogous manner as described in Example 1, thedyestuff produced from p-toluylbenzoylmethane and diazotized 2.4'-dimethyl 5 methoxy- 2' -nitro-4-aminoazobenzene The dyestuff correspondsto the following formula:

In the following table there are given some combinations and the shadesobtained thereby when prepared on celulosic fibres according to thedirections given in Example 1:

ggg g Diazotization component Shade Acetylacetonel.4-diethoxy-2-amino-5-ben- Orange.

zoylaminobenzene. Benzoylacetone- S-nitro-l-aminobenzene Yellow.Diketohydrindene a-aminoanthraquinone Orange. Dibenzoylrnethane1-amino-2-chloro-4-benzoyl- Reddish yelamino-S-methoxybenzene. low. Do2.4-dimethyl--methoxy-2- Orange.

nitro-4 arninoazobenzene. l-amino-2-chloro-4-benzoyl- Reddishyelarnino-5-methylbenzene. low. D0 l-amino-2-methyl-4-benzoyl- Goldenorange.

amino-'5-methoxybenzene. Do 1-amino-2-chloro-4-benzoyl- Golden yellow.amino-fi-etlioxybenzene. Do l-amino-2-methoxy-4-ben- Orange.

zoylamino-iethoxybenzene. D0 l-amino-ZS-dirnethoxy-4- Orange.

benzoylaminobenzene. Do 1-amino-2.5-dietl1oxy-4-ben- Orange.

zoylaminobenzene. D0 l-amino-2-ethoxy-4-benzoyl- Golden yellow.amino-Mnethylbenzene. l-amino- 2 -methoxy 4 ben- Golden yellow.

zoylamino-5-clilorobenzene. I l-amino-2-chlor0-4-benzoyl- Reddishyelaminobenzene. low. l-amino-Z-chloro-l-methyl- Reddisli yelfibenzoylaminobenzene. w. 1-amino-2-methyl-4-chloro- Greenish yel-B-benzoylaminobenzene. low. 1-amino-2-chloro-4-methoxy- Reddish yel-5-benzoylaminobenzene. w. l-amino-Z-methoxy--chloro- Greemsh yel-5-benzoylaminobenzene. low. 2 methylbenzoyl 1-amino-2-methyl-tbenzoyl-Reddish yelbenzoylrnethane. amino-5-chl0robenzene. low. 4 chlorobenzoyl2.5-dichloroaniline Yellow.

benzoylmethane.

Do 1.3 dimetliyl 4 amino 6 Greenlsh yelbenzoylaminobenzene. w. Do2.3'-dimethyl-4-amino- Yellowlsh azobenzene. brown.

We claim:

1. Cellulosic fibers dyed with a water-insoluble azo-dyestuif of thefollowing general formula:

wherein a: and 1/ stand for radicals of the aromatic-,aromatic-aliphaticor aliphatic series, R stands for the radical of adiazotized substituted amine of the aromatic series, and wherein thenuclei bear only substituents which do not cause solubility in water andwhich are selected from the group consisting of alkyl, alkoxy, halogen,nitro and acylamino, the shades produced being generally yellow toorange and being dischargeable to a pure white.

2. Cellulosic fibers dyed with a water-insoluble azo-dyestufi of thefollowing general formula:

wherein a: and 1,! stand for radicals of the phenyl series, R stands forthe radical of a diazotized substituted amine of the aromatic series,and wherein the nuclei bear only substituents which do not causesolubility in water and which are selected from the group consisting ofalkyl, alkoxy, halogen, nitro and acylamino, the shades produced beinggenerally yellow to orange and being dischargeable to a pure white. I

4. Cellulosic fibers dyed with a water-insoluble azo-dyestuff of thefollowing general formula:

wherein a: and y stand for radicals of the phenyl series, B. stands fora substituted radical of the benzeneor naphthalene series, andwhereinthe nuclei bear only substituents which do not cause solubility in waterand which are selected from the group consisting of alkylpalkoxy,halogen,

nitro and acylamino, the shades produced being generally yellow toorange and being dischargeable to a pure white.

5. Cellulosic fibers dyed with a water-insoluble azo-dyestuii oi thefollowing formula:

yielding clear greenish-yellow, dischargeable dyeings of good fastnessto boiling and light.

6. Celluloslc fibers dyed with a water-insoluble azo-dyestufi of thefollowing formula:

yielding clear reddish yellow dyeings of good fastness to boiling andlight.

'7. Cellulosic fibers dyed with a Water-insoluble azo-dyestufi of thefollowing general formula:

wherein a: and y stand for methyl groups, R stands for the radical of adiazotized substituted amine of the aromatic series, and wherein thenuclei may bear substituents selected from the group consisting ofalkyl, alkoxy, halogen, nitro and acylamino, the shades produced beinggenerally yellow to orange and being dischargeable to a pure white.

8. Cellulosic fibers dyed with a water-insoluble azo-dyestufi of thefollowing general formula:

wherein m and 1 stand for methyl groups, R stands for a substitutedradical of the benzeneor naphthalene series, and wherein the nuclei maybear substituents selected from the group consisting of alkyl, alkoxy,halogen, nitro and acylamino, the shades produced being generally 9yellow to orange andbeing dischargeable to a pure white.

ED BERGDOLT. ON OSSENBECK. ERNST TIETZE. I" J G.

